Herbicidal aryl acetylene ethers

ABSTRACT

New compounds represented by the following generic formula:   WHEREIN R can be alkynyl; R1 can be alkynoxy; X can be selected from the group consisting of hydrogen, alkyl, alkynoxy or halogen.

United States Patent 1191 Mihailovski et al. I

[4 June 11, 1974 HERBICIDAL ARYL ACETYLENE ETHERS [76] Inventors: Alexander Mihailovski, 1812 Delaware St., Berkeley, Calif. 91504; Ferenc M. Pallos, 3027 Vessing Rd., Pleasant Hill, Calif. 94523 [22] Filed: Dec. 8, 1972 [21] Appl. No.: 313,376

Related US. Application Data [62] Division of Ser. No. 90,064, Nov. 16, 1970.

Harris ct al..

Sterling et al 7l/l24 X 3, l 3 l l 66 3,340,308

Primary Examiner-Lewis Gotts Assistant Examiner-Catherine L. Mills Attorney, Agent, or Firm-Daniel C. Block 5 7 1 ABSTRACT New compounds represented by the following generic formula:

wherein R can be alkynyl; R, can be alkynory; X can be selected from the group consisting of hydrogen, alkyl, alkynoxy or halogen.

9 Claims, N0 Drawings HERBICIDAL ARYL ACETYLENE ETHERS This is a division of US. Pat. application Ser. No. 90,064, filed NOV. 16, 1970.

DESCRIPTIONOF THE INVENTION This invention is directed. to a novel group of compounds which may be generically described as aryl acetylenes which are active herbicides. The compounds of the present invention are represented by the general formula:

wherein R can be alkynyl; R, can be alkynoxy; X' can be selected from the group consisting of hydrogen, alkyl, alkynoxy or halogen.

The above-noted compounds can be prepared. by treating. a substituted phenol or polyhydroxy benzene: with a propargyl halide in an inert solvent such as acetone, using approximately a. mole equivalent ofa base. as an acid acceptor such as. potassium carbonate.

In order to illustrate. the. merits ofthis invention the following examples are provided:

EXAMPLE 1 l ,4-bis-( 2.'-Butynoxy.)benzene.

A mixture of 10.0 g. (0.047 moles) hydroquinone, 45' ml. methanol, 8.7 g; (0.098amoles). l.-chloro-2-butyne and 20.3' g. of 25 percent sodium methoxideinmethanol (equivalent to 0.094 moles-sodium methoxide.) waspurged with a streamof argon'gasand'thentrefluxedfor four hours. The solvent' was-evaporated. The residue was dissolved in 50 ml. ethyl etherand' thenwashed with percent sodium hydroxide'and'water.After drying. the ether solution was concentrated'andfcooled togive 3.7 g. of crystallineproduct; m'.p. 76.578".5'C. Yield, 37'percent of theory.

EXAMPLE 2.

2,4-bis-( 2.-Propynoxy)bromobenzene To a solution of 10.0 g. (0.053 moles) 4'- bromoresorcinol in 50 ml. acetone which had been" purged with argon gas were added 16.1v g. (0.116 moles) anhydrous potassium carbonate. and 1 329" g. (0.116 moles) propargyl bromide dissolved-irr-25ml. acetone. The resulting mixture was refluxediwith vigorous stirring for 18 hours, then-filtered and-"the solvent evaporated. The residue was dissolved'in ethyl'ether and the othersolution' was washed iwith:5% sodiumhydroxide. After drying the etherfraction with'anhydrous magnesium sulfate, the 'solvent wasevaporated to give a solid product'whichwas recrystallized: from petroleum ether/benzene. Some 6.9 g. of crystalline material were obtained; m.p.- 6l-63 C. Yield, 49 percent of theory. Structural. proof followedfrominfrared and proton magnetic resonancespectroscopy.

Other compounds were prepared in an'analogous: manner starting with the appropriate-reagents as-outlined above. The followingjs a table .of'compoundsirepresentative of thoseembodied by thepresent invention. Compound. numbers have been assigned 1 to tirem and are used for" identification throughout .the; balance..- of the specification.

HERBICIDAL SCREENING TESTS As previously mentioned, the novel compounds herein described are phytotoxic compounds which are useful and valuable in controlling various plant species. Compounds of this invention are tested as herbicides in the following manner.

Pre-Emergence Herbicide Test herbicide test.

On' the. day preceding treatment, seeds of seven different'weed speciesareplantedin individual rows using one. species per row across the width of the flat. The seeds used. are hairy crabgrass (Digigaris Sanguinalis (L.) Scop. yellow foxtail (Setaria glauca (L.) Beauv.

watergrass (Echinochloa crusgalli (L.) Beauv. California red. oat (Avena sativa (L.)), redroot pigweed (Amaranthus retroflxus' (L.)), lndian mustard (Brassica juncea (L.) Coss.) and curly dock (Rumex crispus- (L.)) Amplese'eds areplanted to .give about 20 to 50 seedlings per-row, after emergence, depending on 1 thesize of the. plants. The flats are watered after'planting. The'spraying'solutionis preparedby dissolving 50 mg; of the testicompound in 3ml. of a solvent, such as acetone, containingtl percent Tween 20 (polyoxyethylene.sorbitan'monolaurate). The following day each flat is sprayedat the: rate:- of-20 pounds of the candidate compoundsperBO gallons of solution per acre. An atomizer'is usedftospray theisolution'on' soil surface. The flats are.pl'aced inagreenhouse at F. and watered regularly. Two' weekslater; the degree of weed control is determinedby comparingrtlie amount of germination and 'growth'of 'each'weed in'theitreated flats with weeds in several untreatedtcontrol'flats. Theratingsystem is as follows:

0 nosignificant injury 0-10 percent control) 3i= slightiinjury .10-40 percent control) 6 =-moderate.injury- (40-70 percent control) 9.=severe-winjury ordeath'"(70-lO0 percentcontrol) Anxactivity indxrisusedLto represent thetotal activity on;a]l seven weedspecies. lt'is'the sum'of the'numbers divided'by, so-thatianiactivityindex of 2 l= represents complete. controloftall seven weeds. Theiresults of this test areareportedi in Table. II.

Post-Emergence Herbicide Test herbicide test.

Seeds of fiveweed'species including hairy crabgrass, watergrass, wildoats; lndiammustard, and curly dock and: onecropfi pinto" beans (Phaseolus vulgaris), are planted in flatssas described above *forpre-emergence screening; The. fiatszare: placedjin the greenhouseat 7285? F. andwatereddaily with 'a sprinkler. About 10 to 14 days after planting when theprimary leaves of the beanplant are almost fully expanded and the first trifoliate leaves are just starting to form, the plants are sprayed. The spray is prepared by weighing out 50 mg. of the test compound, dissolving it in 5 ml. of acetone containing 1 percent Tween 20 (polyoxy-ethylene sorbitan monolaurate) and then adding 5 ml. of water. The solution is sprayed on the foliage using an atomizer. The spray concentration is 0.5 percent and the rate would be approximately 20 lb./acre if all of the spray were retained on the plant and the soil, but some spray is lost so it is estimated that the application rate is approximately l2.5 lb./acre.

Beans are used to detect defoliants and plant growth regulators. The beans are trimmed to two or three plants per flat by cutting off the excess weaker plants several days before treatment. The treated plants are placed back in the greenhouse and care is taken to avoid sprinkling the treated foliage with water for three days after treatment. Water is applied to the soil by means of a slow stream from a watering hose taking care not to wet the foliage.

lnjury levels are made and recorded 14 days after treatment. The rating system is the same as described above for the pre-emergence test Wherev (3), (6) and (9) are, used for the different levels of injury and control. The injury symptoms are also recorded. The maximum activity index for complete control of all the species in the post-emergence screening test is 18 which represents the sum of the rating numbers obtained with the six plant species used in the test divided by- 3. The herbicide activity indices are shown in Table ll.

TABLE ll SCREENING RESULTS Compound No. Pre-emergence Post-emergence 1 l0 6 2 l6 9 3 l8 9 4 2| [8 5 l7 l2 6 l7 9 7 l6 1 l 8 l8 l6 What is claimed is:

1. The method of controlling undesirable vegetation comprising applying to the locus where control is desired an herbicidally effective amount of a compound having the generic formula wherein R is selected from the group consisting of propynyl and butynyl; R, is selected from the group consisting of propynoxy and butynoxy; X is selected from the group consisting of hydrogen, methyl, propynoxy, chlorine and bromine.

2. The method as set forth in claim 1 wherein R is CH C I CCH R, is 4-OCH C I CCH, and X is H.

3. The method as set forth in claim 1 wherein R is CH C I CH, R, is 4-OCH C f CH and X is 2,3,5-CH

4. The method as set forth in claim 1 wherein R is -CH C I CH, R, is 2-OCH C CH and X is 3-OCH C 5. The method as set forth in claim 1 wherein R is CH C I CH, R, is 3-OCH C CH and X is 4-Cl. 6. The method as set forth in claim 1 wherein R is CH C CH, R, is 3-OCH C 5 CH and X is 2-CH,,.

7. The method as set forth in claim 1 wherein R is CH C 1 CH, R, is 4-OCH C CH and X is 2-Cl.

8. The method as set forth in claim 1 wherein R is CH C I CH, R, is 4-OCH C I CH and X is 2-Br.

9. The method as set forth in claim 1 wherein R is CH C I CH, R, is 3-OCH C i CH and X is 4-Br.

90-1050 UNITED STATES PATENT OFFICE CERTIFICATE 0F CORRECTION Patent No. 3,816 O91 Dated smil 11! 1974 I Inventor(s) Alexander Mihailovskiet a1.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

r- On Page 1, the title should read -'--ARYL ACETYLENE ETHERS On Page 1, in the. patent heading, the phrase ,l-iiassimiorto Stauffer Chemical Com any,

New York, N. Y. should be added.

In Column 1; line '54, the word "other" should read ---ether'---.,

In Column 2, line 23, the heading "Pre-Emergence Herbicide Test herbicide test" should read ---Pre-Emergence Herbicide Test---.

In Column 2, line 60, the heading "Post-Emergence Herbicide Test herbicide test" should read ---Post-Emergence Herbicide Test- In mm 2 line 66, the figures reading "7285F" should read ----'72-85 F---. a

Signed and sealed this 19th day of November 1974.

(SEAL) Attest:

McCOY M. GIBSON JR. l c. MARSHALL DANN Attesting Officer Commissioner of Patents 

2. The method as set forth in claim 1 wherein R is CH2C*CCH3, R1 is 4-OCH2C*CCH3 and X is H.
 3. The method as set forth in claim 1 wherein R is CH2C*CH, R1 is 4-OCH2C*CH and X is 2,3,5-CH3.
 4. The method as set forth in claim 1 wherein R is CH2C*CH, R1 is 2-OCH2C*CH and X is 3-OCH2C*CH.
 5. The method as set forth in claim 1 wherein R is CH2C*CH, R1 is 3-OCH2C*CH and X is 4-Cl.
 6. The method as set forth in claim 1 wherein R is CH2C*CH, R1 is 3-OCH2C*CH and X is 2-CH3.
 7. The method as set forth in claim 1 wherein R is CH2C*CH, R1 is 4-OCH2C*CH and X is 2-Cl.
 8. The method as set forth in claim 1 wherein R is CH2C*CH, R1 is 4-OCH2C*CH and X is 2-Br.
 9. The method as set forth in claim 1 wherein R is CH2C*CH, R1 is 3-OCH2C*CH and X is 4-Br. 